US11590480B2 - Molecular sieve and its preparation method - Google Patents

Molecular sieve and its preparation method Download PDF

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US11590480B2
US11590480B2 US17/330,137 US202117330137A US11590480B2 US 11590480 B2 US11590480 B2 US 11590480B2 US 202117330137 A US202117330137 A US 202117330137A US 11590480 B2 US11590480 B2 US 11590480B2
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molecular sieve
copper
reaction
hydrothermal synthesis
calculated
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US20210283586A1 (en
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Yan Wang
Zhaoqiang Li
Zhiyong Ding
Rongrong Fan
Cheng Zhang
Yu Wang
Xin Guo
Na Kang
Wei Liu
Rong Wang
Jing Song
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Baotou Rare Earth Research Institute
Ruike National Engineering Research Centre of Rare Earth Metallurgy and Functional Materials Co Ltd
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Baotou Rare Earth Research Institute
Ruike National Engineering Research Centre of Rare Earth Metallurgy and Functional Materials Co Ltd
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F01N3/2066—Selective catalytic reduction [SCR]
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    • B01J2219/1947—Details relating to the geometry of the reactor round oval or ellipsoidal
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    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material

Definitions

  • the present invention relates to a molecular sieve and its preparation method.
  • Zeolite molecular sieve has been widely used in the fields of adsorption, separation and catalysis due to its high stability, regular uniform pores and adjustable acidity and alkalinity.
  • SCR selective catalytic reduction
  • NOx nitrogen oxides
  • transition metals such as copper
  • CN110102337A discloses a preparation method of a composite copper-based SCR molecular sieve catalyst.
  • N,N,N-trimethyl-1-adamantyl ammonium hydroxide is mixed with water during stirring, aluminum sulfate is added during stirring, the pH value is adjusted by an alkali, silica sol is added during stirring, and an initial gel mixture is obtained; the initial gel mixture is crystallized at the constant temperature, cooled, washed, dried and calcined to obtain a CHA-type molecular sieve; the CHA-type molecular sieve is used as a carrier, manganese nitrate, cerium nitrate, palladium nitrate and copper acetate are impregnated stepwise, and then drying is carried out to obtain the composite copper-based SCR molecular sieve catalyst.
  • a CHA-type molecular sieve is firstly synthesized by the hydrothermal method, and then impregnation is performed so that modifying elements are loaded on molecular sieve.
  • the crystal type of the molecular sieve obtained by this method is cube, which results in a poor catalytic performance at a low temperature or a high temperature.
  • CN110252392A discloses a preparation method of a cerium modified Cu-SAPO-34 molecular sieve catalyst.
  • Cu-TEPA is synthesized with a copper source and tetraethylenepentamine, a first gel is prepared with a phosphorus source and an aluminum source; Cu-TEPA is mixed with the first gel, a silicon source and a template to obtain a second gel; a cerium source is added dropwise to the second gel to obtain a third gel; the third gel is transferred to a hydrothermal kettle for crystallization, and the crystallized product is cooled, filtered, washed with water, dried and roasted to obtain Cu-SAPO-34 catalyst partially substituted by cerium.
  • CN108905603A discloses a preparation method of CuCeSAPO-34 molecular sieve.
  • Tetraethylammonium hydroxide is added into deionized water and stirred.
  • aluminum isopropoxide is added till it is completely dissolved.
  • orthophosphoric acid and ethyl orthosilicate are added and stirred to obtain a uniform solution.
  • a cerium salt is added into the uniform solution. After fully stirring the solution and the cerium salt, a copper salt is added and completely stirred to obtain a sol.
  • the sol is added into a hydrothermal reactor for crystallization reaction. After the crystallization reaction is completed, cooling is performed at room temperature.
  • the solid crystallization product is separated from the mother liquor, and washed with deionized water until the solid crystallization product is neutral.
  • the washed solid crystallization product is dried before being calcined in air to obtain the CuCeSAPO-34 molecular sieve.
  • a molecular sieve is synthesized by one-step hydrothermal synthesis method.
  • the crystal structure of obtained molecular sieve is not in a football shape, leading to a poor catalytic performance at a low temperature or a high temperature.
  • the purpose of the present invention is to provide a molecular sieve which has micromorphology in football shape. Further, the molecular sieve has a large specific surface area. Further, the molecular sieve of the present invention has a high catalytic activity in a temperature range of 175-550° C. and a good resistance to hydrothermal aging.
  • Another purpose of the present invention is to provide a method for preparing a molecular sieve, wherein the obtained molecular sieve has micromorphology in football shape. Further, the obtained molecular sieve by this method has a large specific surface area. Further, the obtained molecular sieve by this method has a high catalytic activity in a temperature range of 175-550° C. and a good resistance to hydrothermal aging.
  • the present invention provides a molecular sieve which has micromorphology in a football shape and consists of molecular sieve framework and active elements, wherein the molecular sieve framework comprises silicon element and aluminum element, the active elements comprises copper element and rare earth elements, and the rare earth elements are one or more selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Sc and Y;
  • the mass ratio of the silicon element to the aluminum element is 3-9:1, the content of the copper element in the molecular sieve is 1.5-3.2 wt %, the mass of rare earth elements is 50 ppm-2 wt % of the molecular sieve framework;
  • the mass of the silicon element is calculated by silicon dioxide
  • the mass of aluminum element is calculated by aluminum oxide
  • the mass of copper element is calculated by copper oxides
  • the mass of rare earth elements is calculated by rare earth oxides.
  • the molecular sieve of the present invention preferably, has a pore size less than 0.7 nm, a specific surface area more than 500 m 2 /g, a pore volume of 0.2-1 mL/g, and an acid amount of 0.8-1.5 mmol/g.
  • the molecular sieve of the present invention preferably, the molecular sieve also comprise alkali metal elements, the content of the alkali metal elements is equal to or less than 200 ppm; wherein the mass of the alkali metal elements is calculated by alkali metal oxide.
  • the molecular sieve of the present invention is a CHA-type molecular sieve.
  • the present invention provides a preparation method of the molecular sieve above, which comprises the following steps:
  • step (2) mixing the reaction product obtained in step (1) with an ammonium source and a copper source to obtain a second mixture, and performing the second hydrothermal synthesis reaction;
  • step (3) mixing the reaction product obtained in step (2) with a rare earth source to obtain a third mixture, and performing the third hydrothermal synthesis reaction;
  • step (3) (4) performing solid-liquid separation of the reaction product obtained in step (3), and calcining the obtained solid substance in the reaction product to obtain the molecular sieve.
  • the templates are one or more selected from the group consisting of N,N,N-trimethyl-1-adamantyl ammonium hydroxide, benzyl trimethyl ammonium, copper-tetraethylenepentamine complex, tetraethylammonium hydroxide and tetrapropylammonium hydroxide;
  • the alkali metal inorganic base is one or more selected from the group consisting of lithium hydroxide, sodium hydroxide and potassium hydroxide;
  • the silicon source is one or more selected from the group consisting of silicate esters, silica, fumed silica, silica sol and colloidal silica;
  • the aluminum source is one or more selected from the group consisting of pseudo boehmite, aluminum hydroxide, aluminum sol and sodium metaaluminate;
  • the ammonium source is one or more selected from the group consisting of ammonium nitrate and ammonium chloride;
  • the copper source is one or more selected from the group consisting of copper
  • the molar ratio of the silicon source to the aluminum source is 1-20:1, the molar ratio of the alkali metal inorganic base to the aluminum source is 5.1-15.3:1, the molar ratio of the templates to the aluminum source is 1.0-10:1, and the molar ratio of the water to the aluminum source is 550-1000:1; the molar ratio of the copper source to the aluminum source is 0.6-8:1, the molar ratio of the ammonium source to the aluminum source is 2.1-8:1; the mass of rare earth source is 50 ppm-2 wt % of the solid substance in the reaction product obtained in step (1); wherein the mass of the silicon source is calculated by silicon dioxide, the mass of aluminum source is calculated by aluminum oxide, the mass of alkali metal inorganic base is calculated by alkali metal oxides, the mass of the copper source is calculated by copper oxides, the mass of the ammonium source is calculated by NH 4 + , and the mass of the rare earth source is calculated by rare
  • the temperature of the first hydrothermal synthesis reaction is 80-180° C., and the reaction time is 1-5 days; wherein the temperature of the second hydrothermal synthesis reaction is 40-100° C., and the reaction time is 4-48 h; wherein the temperature of the third hydrothermal synthesis reaction is 40-80° C., and the reaction time is 4-48 h; wherein the solid substance is calcined by a way of microwave roasting, the calcination temperature is 500-800° C. and the calcination time is 3-10 h.
  • the templates, the alkali metal inorganic base and water are mixed at a temperature of 40-80° C. and then mixed with the silicon source and the aluminum source to obtain the first mixture.
  • the solid-liquid separation comprises the following procedure:
  • step (3) filtering and washing the reaction product obtained in step (3), and then drying by a way of microwave drying, where the microwave drying temperature is 60-110° C., the microwave drying time is 3-8 h.
  • a molecular sieve with micromorphology in football shape is prepared with a multi-step hydrothermal synthesis method.
  • the molecular sieve has an ultramicropore structure with a large specific surface area and a high pore volume. Further, the molecular sieve has a high catalytic activity in a temperature range of 175-550° C. and a good resistance to hydrothermal aging.
  • FIG. 1 is the scanning electron microscope photo of the molecular sieve prepared in example 1 of the present invention.
  • FIG. 2 is the scanning electron microscope photo of the molecular sieve prepared in example 2 of the present invention.
  • FIG. 3 is the scanning electron microscope photo of the zeolite molecular sieve containing copper prepared in comparative example 1 of the present invention.
  • FIG. 4 is the XRD pattern of the molecular sieve prepared in example 1 of the present invention.
  • FIG. 5 is the XRD pattern of the molecular sieve prepared in example 2 of the present invention.
  • FIG. 6 is the XRD pattern of the zeolite molecular sieve containing copper prepared in comparative example 1 of the present invention.
  • Specific surface area refers to the total area that per unit mass of material has.
  • Pore size refers to the distance between two opposite walls of a pore.
  • Acid amount refers to the mmol numbers of acid sites on per unit mass of a catalyst.
  • the molecular sieve of the present invention has micromorphology in football shape and consists of molecular sieve framework and active elements.
  • the molecular sieve framework comprises silicon element and aluminum element, the active elements comprise copper element and rare earth elements.
  • the silicon element and the aluminum element exist in the form of atoms, and the copper element and the rare earth elements exist in the form of ions.
  • the crystal of the molecular sieve of the present invention has micromorphology in a football shape.
  • the molecular sieve of the present invention can be CHA-type molecular sieve.
  • the rare earth elements are one or more selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Sc and Y.
  • the rare earth elements are one selected from the group consisting of Ce and Y. More preferably, the rare earth element is Ce.
  • the mass ratio of the silicon element to the aluminum element is 3-9:1.
  • the mass ratio of the silicon element to the aluminum element is 5-9:1. More preferably, the mass ratio of the silicon element to the aluminum element is 8-9:1.
  • the mass of the silicon element is calculated by silicon dioxide, and the mass of aluminum element is calculated by aluminum oxide. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the content of the copper element in the molecular sieve is 1.5-3.2 wt %; preferably, 1.5-2.5 wt %; more preferably, 2.2-2.5 wt %.
  • the mass of copper element is calculated by copper oxides. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the mass of rare earth elements is 50 ppm-2 wt % of the molecular sieve framework; preferably, 50 ppm-500 ppm; more preferably, 100 ppm-250 ppm.
  • the mass of rare earth elements is calculated by rare earth oxides. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the molecular sieve of the present invention may also comprise alkali metal elements in a small amount, such as Na, K and the like.
  • the content of the alkali metal elements may be less than or equal to 200 ppm.
  • the content of the alkali metal elements is less than or equal to 150 ppm. More preferably, the content of the alkali metal elements is less than or equal to 100 ppm.
  • the mass of the alkali metal elements is calculated by alkali metal oxide.
  • the molecular sieve of the present invention has an ultramicropore structure, and its pore size is less than 0.7 nm.
  • the pore size of the molecular sieve is less than 0.65 nm. More preferably, the pore size of the molecular sieve is 0.6-0.65 nm.
  • the molecular sieve of the present invention has a specific surface area more than 500 m 2 /g.
  • the molecular sieve has a specific surface area more than 600 m 2 /g. More preferably, the molecular sieve has a specific surface area more than 700 m 2 /g.
  • the molecular sieve of the present invention has a pore volume of 0.2-1 mL/g; preferably, 0.5-1 mL/g; more preferably, 0.7-1 mL/g.
  • the molecular sieve of the present invention has an acid amount of 0.8-1.5 mmol/g; preferably, 1-1.5 mmol/g; more preferably, 1.2-1.5 mmol/g.
  • the molecular sieve catalyst of the present invention has a broader temperature window.
  • the conversion rate of nitrogen oxide is more than 89%; preferably, the conversion rate of nitrogen oxide is more than 90%; more preferably, the conversion rate of nitrogen oxide is more than 92.5%.
  • the preparation method of molecular sieve of the present invention comprises the following steps: (1) first hydrothermal synthesis reaction step; (2) second hydrothermal synthesis reaction step; (3) third hydrothermal synthesis reaction step; (4) calcination step.
  • the composition and properties of the obtained molecular sieve are as described previously. Detailed description is given below.
  • Templates an alkali metal inorganic base, a silicon source, an aluminum source and water are used to prepare a first mixture, and the first hydrothermal synthesis reaction is carried out.
  • the aluminum source of the present invention may be one or more selected from the group consisting of pseudo boehmite, aluminum hydroxide, aluminum sol and sodium metaaluminate.
  • the aluminum source is one or more selected from the group consisting of aluminum sol and sodium metaaluminate. More preferably, the aluminum source is selected from the group consisting of sodium metaaluminate.
  • the aluminum sol may have a content of 5-15 wt %, pH of 3-5, viscosity of 35-50 mPa ⁇ s and a particle size of 5-15 nm.
  • the templates of the present invention may be one or more selected from the group consisting of N,N,N-trimethyl-1-adamantyl ammonium hydroxide, benzyl trimethyl ammonium, copper-tetraethylenepentamine complex, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
  • the templates are one or more selected from the group consisting of N,N,N-trimethyl-1-adamantyl ammonium hydroxide, benzyl trimethyl ammonium, copper-tetraethylenepentamine complex. More preferably, the template is N,N,N-trimethyl-1-adamantyl ammonium hydroxide.
  • the molar ratio of the templates to the aluminum source may be 1.0-10:1; preferably, 1.3-8:1; more preferably, 1.3-6:1.
  • the aluminum source is calculated by aluminum oxide. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the silicon source of the present invention may be one or more selected from the group consisting of silicate esters, silica, fumed silica, silica sol and colloidal silica.
  • the silicon source is one or more selected from the group consisting of silica sol and colloidal silica.
  • the silicon source is silica sol.
  • the silica sol may have a solid content of 15-25 wt %, pH of 3-6, a density of 1-2 g/cm 3 and a particle size of 8-15 nm.
  • the molar ratio of the silicon source to the aluminum source may be 1-20:1; preferably, 10-20:1; more preferably, 12-18:1.
  • the silicon source is calculated by silicon dioxide, and the aluminum source is calculated by aluminum oxide. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the alkali metal inorganic base of the present invention may be alkali metal hydroxide.
  • the example of the alkali metal hydroxide includes but is not limited to lithium hydroxide, sodium hydroxide or potassium hydroxide.
  • the alkali metal inorganic base is one or more selected from the group consisting of sodium hydroxide and potassium hydroxide. More preferably, the alkali metal inorganic base is sodium hydroxide.
  • the molar ratio of the alkali metal inorganic base to the aluminum source may be 5.1-15.3:1; preferably, 6-12:1; more preferably, 7-10:1.
  • the alkali metal inorganic base is calculated by alkali metal oxides, and the aluminum source is calculated by aluminum oxide. In such a way, the molecular sieve with micromorphology in football shape may be obtained. Preferably, the molecular sieve with crystal morphology in football shape may be obtained.
  • the molar ratio of the water to the aluminum source may be 550-1000:1; preferably, 700-900:1; more preferably, 800-900:1.
  • the temperature of the first hydrothermal synthesis reaction may be 80-180° C.; preferably, 100-150° C.; more preferably, 100-120° C.
  • the reaction time of the first hydrothermal synthesis reaction may be 1-5 days; preferably, 1-4 days; more preferably, 1-2 days.
  • the molecular sieve with micromorphology in football shape may be obtained.
  • the molecular sieve with crystal morphology in football shape may be obtained.
  • the templates, the alkali metal inorganic base and water are mixed before mixing with the silicon source and the aluminum source to obtain the first mixture.
  • the templates, the alkali metal inorganic base and water may be mixed at a temperature of 40-80° C.
  • the templates, the alkali metal inorganic base and water may be mixed at a temperature of 50-70° C.
  • the templates, the alkali metal inorganic base and water may be mixed with heating under reflux.
  • step (1) The reaction product obtained in step (1) is mixed with an ammonium source and a copper source to obtain a second mixture, and the second hydrothermal synthesis reaction is carried out.
  • the ammonium source is one or more selected from the group consisting of ammonium nitrate and ammonium chloride.
  • the ammonium source is ammonium nitrate.
  • the molar ratio of the ammonium source to the aluminum source is 2.1-8:1; preferably, 4-8:1; more preferably, 4-7:1.
  • the ammonium source is calculated by NH 4 +
  • the aluminum source is calculated by aluminum oxide. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the copper source is one or more selected from the group consisting of copper nitrate, copper sulfate, copper chloride, copper gluconate, copper propionate, copper acetate, copper isopropate and copper-glutamate chelate.
  • the copper source is one or more selected from the group consisting of copper-glutamate chelate and copper acetate. More preferably, the copper source is copper-glutamate chelate.
  • the molar ratio of the copper source to the aluminum source is 0.6-8:1; preferably, 4-8:1; more preferably, 4-7:1.
  • the copper source is calculated by copper oxides, and the aluminum source is calculated by aluminum oxide. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the temperature of the second hydrothermal synthesis reaction may be 40-100° C.; preferably, 50-90° C.; more preferably, 70-90° C.
  • the reaction time of the second hydrothermal synthesis reaction may be 4-48 h; preferably, 4-20 h; more preferably, 8-15 h. In such a way, the molecular sieve with micromorphology in football shape may be obtained, and the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the reaction product obtained in step (1) is cooled down to 20-35° C., and then is mixed and stirred with an ammonium source for 3-15 h to obtain mixture A; and then mixture A is mixed and stirred with a copper source for 1-5 h to obtain a second mixture.
  • the reaction product obtained in step (1) is cooled down to 25-30° C., and then is mixed and stirred with an ammonium source for 5-10 h to obtain mixture A; and then mixture A is mixed and stirred with a copper source for 2-4 h to obtain a second mixture.
  • step (2) The reaction product obtained in step (2) is mixed with a rare earth source to obtain a third mixture, and the third hydrothermal synthesis reaction is carried out.
  • the rare earth source is one or more selected from the group consisting of rare earth oxide, rare earth nitrate and rare earth acetate.
  • the rare earth element is one or more selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Sc and Y.
  • the rare earth element is one selected from the group consisting of Ce and Y. More preferably, the rare earth element is Ce. In such a way, the molecular sieve with micromorphology in football shape may be obtained, and the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the mass of rare earth source is 50 ppm-2 wt % of the solid substance in the reaction product obtained in step (1); preferably, 100 ppm-250 ppm. In such a way, the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • the temperature of the third hydrothermal synthesis reaction may be 40-80° C.; preferably, 50-70° C.; more preferably, 55-65° C.
  • the reaction time of the third hydrothermal synthesis reaction may be 4-48 h; preferably, 8-20 h; more preferably, 8-15 h. In such a way, the molecular sieve with micromorphology in football shape may be obtained, and the specific surface area and the catalytic activity of the molecular sieve can be increased.
  • step (3) The solid-liquid separation of the reaction product obtained in step (3) is carried out, and the obtained solid substance is calcined to obtain the molecular sieve.
  • the solid substance is calcined by a way of microwave roasting.
  • the calcination temperature may be 500-800° C.; preferably, 500-700° C.; more preferably, 500-600° C.
  • the calcination time may be 3-10 h; preferably, 3-8 h; more preferably, 3-6 h.
  • the reaction product obtained in step (3) is filtered and washed, and then is dried by a way of microwave drying to obtain solid substance, where the microwave drying temperature is 60-110° C., the microwave drying time is 3-8 h.
  • the reaction product obtained in step (3) is filtered and washed, and then is dried by a way of microwave drying to obtain solid substance, where the microwave drying temperature is 70-90° C., the microwave drying time is 4-6 h.
  • TMAda-OH N,N,N-trimethyl-1-adamantyl ammonium hydroxide
  • 4.8 g of sodium hydroxide and 85 g of water were heated at 60° C. under reflux so as to be mixed uniformly, and then were mixed and stirred for 2 h with 32.9 g of silica sol (a solid content of 20 wt %, pH of 3.2, density of 1.2 g/cm 3 , particle size of 11 nm) and 1.17 g of sodium metaaluminate to obtain a first mixture.
  • the first mixture was subjected to the first hydrothermal synthesis reaction, where the reaction temperature was 110° C., the reaction time was 2 days.
  • step (2) The reaction product obtained in step (1) was cooled down to 30° C., and then was mixed and stirred with 3.43 g of ammonium nitrate for 8 h, and 8.9 g of copper-glutamate chelate was added and stirred for 3 h, so as to obtain a second mixture.
  • the second mixture was subjected to the second hydrothermal synthesis reaction, where the reaction temperature was 80° C., the reaction time was 10 h.
  • step (3) The reaction product obtained in step (2) was mixed and stirred with 0.002 g of cerium oxide for 6 h to obtain a third mixture.
  • the third mixture was subjected to the third hydrothermal synthesis reaction, where the reaction temperature was 60° C., the reaction time was 12 h.
  • step (3) The reaction product obtained in step (3) was cooled down to room temperature, filtered and washed, and then the obtained solid substance was dried by a way of microwave drying at 80° C. for 5 h, subsequently, the dried solid substance was calcined by a way of microwave drying at 550° C. for 4 h to obtain a molecular sieve, which was a CHA-type molecular sieve.
  • TMAda-OH N,N,N-trimethyl-1-adamantyl ammonium hydroxide
  • aqueous solution of N,N,N-trimethyl-1-adamantyl ammonium hydroxide (TMAda-OH) a concentration of 25 wt %)
  • 6.72 g of potassium hydroxide and 85 g of water were heated at 50° C. under reflux so as to be mixed uniformly, and then were mixed and stirred for 3 h with 28.5 g of silica sol (a solid content of 20 wt %, pH of 5.6, density of 1.5 g/cm 3 , particle size of 11 nm) and 7.28 g of aluminum sol (a solid content of 10 wt %, pH of 4, viscosity of 43 mPa ⁇ s, particle size of 10 nm) to obtain a first mixture.
  • the first mixture was subjected to the first hydrothermal synthesis reaction, where the reaction temperature was 130° C., the reaction time was 3 days.
  • step (2) The reaction product obtained in step (1) was cooled down to 25° C., and then was mixed and stirred with 4.57 g of ammonium nitrate for 8 h, and 8.6 g of copper acetate was added and stirred for 3 h, so as to obtain a second mixture.
  • the second mixture was subjected to the second hydrothermal synthesis reaction, where the reaction temperature was 70° C., the reaction time was 13 h.
  • step (3) The reaction product obtained in step (2) was mixed and stirred with 0.004 g of yttrium oxide for 6 h to obtain a third mixture.
  • the third mixture was subjected to the third hydrothermal synthesis reaction, where the reaction temperature was 60° C., the reaction time was 12 h.
  • step (3) The reaction product obtained in step (3) was cooled down to room temperature, filtered and washed, and then the obtained solid substance was dried by a way of microwave drying at 80° C. for 5 h, subsequently, the dried solid substance was calcined by a way of microwave drying at 550° C. for 4 h to obtain a molecular sieve, which was a CHA-type molecular sieve.
  • TMAda-OH N,N,N-trimethyl-1-adamantyl ammonium hydroxide
  • silica sol a solid content of 20 wt %, pH of 3.2, density of 1.2 g/cm 3 , particle size of 11 nm
  • 1.17 g of sodium metaaluminate were mixed and stirred for 2 h to obtain a mixture.
  • the mixture was subjected to hydrothermal synthesis reaction, where the reaction temperature was 110° C., the reaction time was 2 days.
  • reaction product was cooled down to room temperature and filtered, the solid substance was washed with deionized water for three times, and then dried at 80° C. for 5 h before calcining at 550° C. for 4 h, so as to obtain first product.
  • Specific surface area, pore size and pore volume the specific surface area of the catalyst was measured by ASAP 2020HD88 from Micromeritics. During the measurement, the degassing temperature was 105° C. and the degassing time was 2 h. The measurement was repeated for three times, and an average value was taken. The results are shown in Table 1.
  • Acid amount measurement the ammonia adsorption and desorption performance of the catalyst were measured by a chemical adsorption instrument Quantachrome ASAP 292011 from US. The acid amount was calculated based on the area of ammonia desorption peak. The acid amount may be used to measure the ammonia storage performance of the catalyst. The results are shown in Table 1.
  • Morphology measurement Sigma 500 field emission scanning electron microscope from Zeiss, Germany was used to measure the micromorphology of the catalyst. A thin layer of platinum was sprayed on the surface of the sample before testing to improve the conductivity of the sample surface. The results are shown in FIGS. 1 - 3 .
  • Method of determining the denitration performance Gas composition of the reaction (volume ratio): 500 ppm NO, 500 ppm NH 3 , 12% 02, 10% H 2 O, CO 2 8%, CO 800 ppm, C 3 H 6 80 ppm (C3), N 2 as equilibrium gas, gas hourly space velocity (GHSV) of 220000 h ⁇ 1 ; and the volume ratio of NH 3 /NO was 1.
  • the gas detection system was a Fourier infrared analyzer.
  • the conditions of the hydrothermal aging of the catalyst the catalyst was aged at 850° C. for 10 h, and the water content was 10 vol % of the total gas volume.
  • the catalytic performance of fresh catalyst is shown in Table 2, and that of aged catalyst is shown in Table 3.
  • the mass of the silicon element is calculated by silicon dioxide
  • the mass of the aluminum element is calculated by aluminum oxide
  • the content of the copper element is calculated by copper oxides
  • the content of the rare earth elements is calculated by rare earth oxides.
  • the molecular sieve of the present invention has excellent denitration performance in both of low temperature region (below 200° C.) and high temperature region (above 500° C.), and its denitration performance decreases slightly after hydrothermal aging of 850° C./10 h.

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Families Citing this family (14)

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Publication number Priority date Publication date Assignee Title
CN114522722B (zh) * 2022-02-25 2023-07-07 中国地质科学院矿产综合利用研究所 一种稀土介孔分子筛及其制备方法和含分子筛的催化剂
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CN118698592A (zh) * 2024-06-07 2024-09-27 天津大学 耐高温分子筛限域金属催化剂及其制备方法和应用
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CN120817713B (zh) * 2025-08-19 2025-11-18 常州厚发环保科技有限公司 一种应用于含铜污泥无焰燃烧过程的固化材料及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108905603A (zh) 2018-06-06 2018-11-30 清华大学盐城环境工程技术研发中心 CuCeSAPO-34分子筛的制备方法及产品和用途
CN110102337A (zh) 2019-06-06 2019-08-09 安徽纳蓝环保科技有限公司 一种复合铜基scr分子筛催化剂的制备方法
CN110252392A (zh) 2019-07-18 2019-09-20 付华 一种铈改性的Cu-SAPO-34分子筛催化剂及其制备方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101031511B (zh) * 2004-10-01 2010-06-30 埃克森美孚化学专利公司 铝磷酸盐分子筛、其合成及用途
WO2010121257A1 (en) * 2009-04-17 2010-10-21 Johnson Matthey Public Limited Company Small pore molecular sieve supported copper catalysts durable against lean/rich aging for the reduction of nitrogen oxides
CN102464337A (zh) * 2010-11-10 2012-05-23 中国科学院大连化学物理研究所 一种含稀土zsm-35分子筛的绿色合成方法
JP6324895B2 (ja) * 2011-11-11 2018-05-16 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ゼオライト系材料の製造方法、合成ゼオライト系材料及び合成ゼオライト系材料の使用方法
WO2014015304A1 (en) * 2012-07-19 2014-01-23 University Of Houston System Methods of controlling polymorphism in organic-free synthesis of na-zeolites and zeolite crystals formed therefrom
JP6599637B2 (ja) * 2015-05-13 2019-10-30 イビデン株式会社 ゼオライト、該ゼオライトの製造方法、該ゼオライトを使用したハニカム触媒及び排ガス浄化装置
CN109195911B (zh) * 2016-05-23 2023-04-07 东曹株式会社 Cha型沸石和其制造方法
JP6792425B2 (ja) * 2016-11-21 2020-11-25 イビデン株式会社 ゼオライトの製造方法
EP3574995B1 (de) * 2017-02-20 2023-08-09 Cataler Corporation Abgasreinigungskatalysator
JP6964479B2 (ja) * 2017-10-03 2021-11-10 エヌ・イーケムキャット株式会社 希土類元素骨格置換ゼオライト及びその製造方法、並びにこれらを用いたＮＯｘ吸着材、選択的還元触媒及び自動車排ガス触媒
CN108786911A (zh) * 2018-05-18 2018-11-13 中触媒新材料股份有限公司 一种含稀土的Cu-AEI分子筛催化剂及其制备方法
JP7412354B2 (ja) * 2018-05-25 2024-01-12 ビーエーエスエフ ソシエタス・ヨーロピア アルミニウムに富む希土類元素含有ゼオライト材料
CN109317191B (zh) * 2018-11-19 2021-06-08 包头稀土研究院 分子筛催化剂及其制备方法和用途
CN109867294A (zh) * 2019-03-19 2019-06-11 南开大学 含铜cha型沸石、其制造方法和用途
CN111135860B (zh) * 2020-02-17 2023-08-04 中国科学院生态环境研究中心 一种稀土金属修饰Cu-SSZ-13分子筛及其制备方法和应用
CN111203269B (zh) * 2020-04-21 2020-09-08 稀土催化创新研究院(东营)有限公司 一种多金属-cha型分子筛催化剂及其制备方法和应用
CN114602544A (zh) * 2022-03-29 2022-06-10 潍柴动力股份有限公司 一种改性Cu-CHA分子筛复合催化剂及其制备方法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108905603A (zh) 2018-06-06 2018-11-30 清华大学盐城环境工程技术研发中心 CuCeSAPO-34分子筛的制备方法及产品和用途
CN110102337A (zh) 2019-06-06 2019-08-09 安徽纳蓝环保科技有限公司 一种复合铜基scr分子筛催化剂的制备方法
CN110252392A (zh) 2019-07-18 2019-09-20 付华 一种铈改性的Cu-SAPO-34分子筛催化剂及其制备方法

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